Stress regulated semiconductor devices and associated methods

ABSTRACT

Stress regulated semiconductor devices and associated methods are provided. In one aspect, for example, a stress regulated semiconductor device can include a semiconductor layer, a stress regulating interface layer including a carbon layer formed on the semiconductor layer, and a heat spreader coupled to the carbon layer opposite the semiconductor layer. The stress regulating interface layer is operable to reduce the coefficient of thermal expansion difference between the semiconductor layer and the heat spreader to less than or equal to about 10 ppm/° C.

PRIORITY DATA

This application is a continuation-in-part of U.S. patent application Ser. No. 13/284,900, filed on Oct. 29, 2011, which claims the benefit of U.S. Provisional Patent Application Ser. No. 61/408,447, filed on Oct. 29, 2010, and which is a continuation-in-part of U.S. patent application Ser. No. 13/239,189, filed on Sep. 21, 2011, which claims the benefit of U.S. Provisional Patent Application Ser. Nos. 61/384,976 and 61/468,917, filed on Sep. 21, 2010 and Mar. 29, 2011 respectively. This application is also a continuation-in-part of U.S. patent application Ser. No. 13/344,527, filed on Jan. 5, 2012, which claims the benefit of the Taiwan Patent Application Serial Number 100100357, filed on Jan. 5, 2011. All of the aforementioned patent applications are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates generally to semiconductor devices and associated methods. Accordingly, the present invention involves the electrical and material science fields.

BACKGROUND OF THE INVENTION

In many developed countries, major portions of the populations consider electronic devices to be integral to their lives. Such increasing use and dependence has generated a demand for electronics devices that are smaller and faster. As electronic circuitry increases in speed and decreases in size, cooling of such devices becomes problematic.

Electronic devices generally contain printed circuit boards having integrally connected electronic components that allow the overall functionality of the device. These electronic components, such as processors, transistors, resistors, capacitors, light-emitting diodes (LEDs), etc., generate significant amounts of heat. As it builds, heat can cause various thermal problems associated with such electronic components. Significant amounts of heat can affect the reliability of an electronic device, or even cause it to fail by, for example, causing burn out or shorting both within the electronic components themselves and across the surface of the printed circuit board. Thus, the buildup of heat can ultimately affect the functional life of the electronic device. This is particularly problematic for electronic components with high power and high current demands, as well as for the printed circuit boards that support them.

Various cooling devices have been employed such as fans, heat sinks, Peltier and liquid cooling devices, etc., as means of reducing heat buildup in electronic devices. As increased speed and power consumption cause increasing heat buildup, such cooling devices generally must increase in size to be effective and may also require power to operate. For example, fans must be increased in size and speed to increase airflow, and heat sinks must be increased in size to increase heat capacity and surface area. The demand for smaller electronic devices, however, not only precludes increasing the size of such cooling devices, but may also require a significant size decrease.

SUMMARY OF THE INVENTION

Accordingly, the present invention provides stress regulated semiconductor devices and associated methods thereof. In one aspect, for example, a stress regulated semiconductor device can include a semiconductor layer, a stress regulating interface layer including a carbon layer bonded to the semiconductor layer by a carbide former, and a heat spreader coupled to the stress regulating interface layer opposite the semiconductor layer. The stress regulating interface layer is operable to reduce the coefficient of thermal expansion difference between the semiconductor layer and the heat spreader to less than or equal to about 10 ppm/° C. In another aspect, the stress regulating interface layer is operable to reduce the coefficient of thermal expansion difference between the semiconductor layer and the heat spreader to less than or equal to about 5 ppm/° C.

A variety of semiconductor materials are contemplated from which the devices according to aspects of the present invention can be constructed. In one aspect, nonlimiting examples of semiconductor materials can include silicon, silicon carbide, silicon germanium, gallium arsenide, gallium nitride, germanium, zinc sulfide, gallium phosphide, gallium antimonide, gallium indium arsenide phosphide, aluminum phosphide, aluminum arsenide, aluminum gallium arsenide, gallium nitride, boron nitride, aluminum nitride, indium arsenide, indium phosphide, indium antimonide, indium nitride, and the like, including composites thereof. In one specific aspect, the semiconductor material can include gallium nitride, aluminum nitride, and composites thereof.

Various carbon materials are also contemplated for inclusion in the carbon layers according to aspects of the present invention. Nonlimiting examples can include diamond-like carbon, boron-doped diamond, amorphous diamond, crystalline diamond, polycrystalline diamond, graphite, and the like, including combinations thereof. In one specific aspect, the carbon layer has an amorphous atomic structure. In another specific aspect the carbon layer is diamond-like carbon. In yet another specific aspect the carbon layer is boron-doped diamond.

Various materials are contemplated for use in the heat spreader layers according to various aspects of the present invention. Nonlimiting examples can include aluminum, copper, tin, tungsten, nickel, titanium, gold, silver, platinum, Al₂O₃, AN, Si₃N₄, Si, glass, and combinations and alloys thereof, and the like, including alloys and mixtures thereof. In one specific aspect the heat spreader includes copper.

In another aspect, a reflective layer disposed between the carbon layer and the semiconductor layer. In a more specific aspect, a carbide former layer can be disposed between the carbon layer and the reflective layer. In yet another aspect, a carbide former layer can be disposed between the carbon layer and the heat spreader layer.

In another aspect of the present invention, a stress regulated semiconductor device is provided. Such a device can include a semiconductor layer and a heat spreader formed on the semiconductor layer, where the heat spreader includes diamond particles uniformly disposed within a metal matrix. The diamond particles are operable to reduce the coefficient of thermal expansion difference between the semiconductor layer and the metal matrix to less than or equal to about 10 ppm/° C. In another aspect, the diamond particles are operable to reduce the coefficient of thermal expansion difference between the semiconductor layer and the metal matrix to less than or equal to about 5 ppm/° C.

In yet another aspect of the present invention, a stress regulated semiconductor device is provided. Such a device can include a semiconductor layer, an electrically conductive boron nitride layer formed on the semiconductor layer, and a heat spreader coupled to the boron nitride layer opposite the semiconductor layer. The boron nitride layer is operable to reduce the coefficient of thermal expansion difference between the semiconductor layer and the heat spreader to less than or equal to about 10 ppm/° C.

In a further aspect of the present invention, a method for reducing stress induced defects in a semiconductor device is provided. Such a method can include forming a stress regulating interface layer including a carbon layer on a semiconductor layer, and coupling a heat spreader layer to the stress regulating interface layer opposite the semiconductor layer. In some aspects, coupling the heat spreader to the stress regulating interface layer includes forming the heat spreader on the stress regulating interface layer. The stress regulating interface layer reduces the coefficient of thermal expansion difference between the semiconductor layer and the heat spreader to less than or equal to about 10 ppm/° C. In another aspect, the method can further include forming a reflective layer between the stress regulating interface layer and the semiconductor layer. In a more specific aspect, the method can further include forming a carbide former layer between the carbon layer and the reflective layer. In yet another aspect, the method can include forming a carbide former layer between the carbon layer and the metal heat spreader layer.

In another aspect of the present invention, a stress regulated light-emitting semiconductor device is provided. Such a device can include a light-emitting semiconductor material, a carbon layer formed on the semiconductor material, and a metal heat spreader coupled to the carbon layer, wherein the carbon layer is operable to reduce the coefficient of thermal expansion difference between the semiconductor layer and the metal heat spreader to less than or equal to about 10 ppm/° C. In one aspect, the metal heat spreader is formed on the carbon layer.

There has thus been outlined, rather broadly, various features of the invention so that the detailed description thereof that follows may be better understood, and so that the present contribution to the art may be better appreciated. Other features of the present invention will become clearer from the following detailed description of the invention, taken with the accompanying claims, or may be learned by the practice of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-section view of a stress regulated semiconductor device in accordance with one embodiment of the present invention.

FIG. 2 is a cross-section view of a stress regulated semiconductor device in accordance with another embodiment of the present invention.

FIG. 3 is a cross-section view of a stress regulated semiconductor device in accordance with yet another embodiment of the present invention.

FIG. 4 is a cross-section view of a stress regulated semiconductor device in accordance with another embodiment of the present invention.

FIG. 5 is a cross-section view of a stress regulated semiconductor device in accordance with yet another embodiment of the present invention.

FIG. 6 is a cross-section view of a stress regulated semiconductor device in accordance with another embodiment of the present invention.

FIG. 7 is a cross-section view of a stress regulated semiconductor device in accordance with another embodiment of the present invention.

FIG. 8 is a cross-section view of a stress regulated semiconductor device in accordance with yet another embodiment of the present invention.

FIG. 9 is a cross-section view of a stress regulated semiconductor device in accordance with another embodiment of the present invention.

FIG. 10 is a cross-section view of a stress regulated semiconductor device in accordance with yet another embodiment of the present invention.

FIGS. 11A and B are SEM photos showing the peeling between plated metal and a semiconductive layer that can occur in a conventional LED;

FIG. 12 is a schematic view of an electron image of a vertical LED in accordance with yet another embodiment of the present invention.

FIG. 13 shows data comparing the thermal expansion coefficient and the thermal conductivity coefficient of a diamond-Cu composite layer in accordance with yet another embodiment of the present invention.

FIG. 14 provides data showing the CTE of a composite material as a function of diamond vol % and Ti wt % in accordance with yet another embodiment of the present invention.

FIG. 15 provides data showing the CTE of a composite material as a function of diamond size in accordance with yet another embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION Definitions

In describing and claiming the present invention, the following terminology will be used in accordance with the definitions set forth below.

The singular forms “a,” “an,” and, “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a dopant” includes reference to one or more of such dopants, and reference to “the diamond layer” includes reference to one or more of such layers.

As used herein, “vapor deposited” refers to materials which are formed using vapor deposition techniques. “Vapor deposition” refers to a process of forming or depositing materials on a substrate through the vapor phase. Vapor deposition processes can include any process such as, but not limited to, chemical vapor deposition (CVD) and physical vapor deposition (PVD). A wide variety of variations of each vapor deposition method can be performed by those skilled in the art. Examples of vapor deposition methods include hot filament CVD, rf-CVD, laser CVD (LCVD), laser ablation, conformal diamond coating processes, metal-organic CVD (MOCVD), sputtering, thermal evaporation PVD, ionized metal PVD (IMPVD), electron beam PVD (EBPVD), reactive PVD, cathodic arc, and the like.

As used herein, “chemical vapor deposition,” or “CVD” refers to any method of chemically forming or depositing diamond particles in a vapor form upon a surface. Various CVD techniques are well known in the art.

As used herein, “physical vapor deposition,” or “PVD” refers to any method of physically forming or depositing diamond particles in a vapor form upon a surface. Various PVD techniques are well known in the art.

As used herein, “diamond” refers to a crystalline structure of carbon atoms bonded to other carbon atoms in a lattice of tetrahedral coordination known as sp³ bonding. Specifically, each carbon atom is surrounded by and bonded to four other carbon atoms, each located on the tip of a regular tetrahedron. Further, the bond length between any two carbon atoms is 1.54 angstroms at ambient temperature conditions, and the angle between any two bonds is 109 degrees, 28 minutes, and 16 seconds although experimental results may vary slightly. The structure and nature of diamond, including its physical and electrical properties are well known in the art.

As used herein, “distorted tetrahedral coordination” refers to a tetrahedral bonding configuration of carbon atoms that is irregular, or has deviated from the normal tetrahedron configuration of diamond as described above. Such distortion generally results in lengthening of some bonds and shortening of others, as well as the variation of the bond angles between the bonds. Additionally, the distortion of the tetrahedron alters the characteristics and properties of the carbon to effectively lie between the characteristics of carbon bonded in sp³ configuration (i.e. diamond) and carbon bonded in sp² configuration (i.e. graphite). One example of material having carbon atoms bonded in distorted tetrahedral bonding is amorphous diamond.

As used herein, “diamond-like carbon” refers to a carbonaceous material having carbon atoms as the majority element, with a substantial amount of such carbon atoms bonded in distorted tetrahedral coordination. Diamond-like carbon (DLC) can typically be formed by PVD processes, although CVD or other processes could be used such as vapor deposition processes. Notably, a variety of other elements can be included in the DLC material as either impurities, or as dopants, including without limitation, hydrogen, sulfur, phosphorous, boron, nitrogen, silicon, tungsten, etc.

As used herein, “amorphous diamond” refers to a type of diamond-like carbon having carbon atoms as the majority element, with a substantial amount of such carbon atoms bonded in distorted tetrahedral coordination. In one aspect, the amount of carbon in the amorphous diamond can be at least about 90%, with at least about 20% of such carbon being bonded in distorted tetrahedral coordination. Amorphous diamond also has a higher atomic density than that of diamond (176 atoms/cm³). Further, amorphous diamond and diamond materials contract upon melting.

The terms “heat transfer,” “heat movement,” and “heat transmission” can be used interchangeably, and refer to the movement of heat from an area of higher temperature to an area of cooler temperature. It is intended that the movement of heat include any mechanism of heat transmission known to one skilled in the art, such as, without limitation, conductive, convective, radiative, etc.

As used herein, “light-emitting surface” refers to a surface of a device or object from which light is intentionally emitted. Light may include visible light and light within the ultraviolet spectrum. An example of a light-emitting surface may include, without limitation, a nitride layer of an LED, or of semiconductor layers to be incorporated into an LED, from which light is emitted.

As used herein, “substrate” refers to a support surface to which various materials can be joined in forming a semiconductor or semiconductor-on-diamond device. The substrate may be any shape, thickness, or material, required in order to achieve a specific result, and includes but is not limited to metals, alloys, ceramics, and mixtures thereof. Further, in some aspects, the substrate may be an existing semiconductor device or wafer, or may be a material which is capable of being joined to a suitable device.

As used herein, the term “substantially” refers to the complete or nearly complete extent or degree of an action, characteristic, property, state, structure, item, or result. For example, an object that is “substantially” enclosed would mean that the object is either completely enclosed or nearly completely enclosed. The exact allowable degree of deviation from absolute completeness may in some cases depend on the specific context. However, generally speaking the nearness of completion will be so as to have the same overall result as if absolute and total completion were obtained. The use of “substantially” is equally applicable when used in a negative connotation to refer to the complete or near complete lack of an action, characteristic, property, state, structure, item, or result. For example, a composition that is “substantially free of” particles would either completely lack particles, or so nearly completely lack particles that the effect would be the same as if it completely lacked particles. In other words, a composition that is “substantially free of” an ingredient or element may still actually contain such item as long as there is no measurable effect thereof.

As used herein, the term “about” is used to provide flexibility to a numerical range endpoint by providing that a given value may be “a little above” or “a little below” the endpoint.

As used herein, a plurality of items, structural elements, compositional elements, and/or materials may be presented in a common list for convenience. However, these lists should be construed as though each member of the list is individually identified as a separate and unique member. Thus, no individual member of such list should be construed as a de facto equivalent of any other member of the same list solely based on their presentation in a common group without indications to the contrary.

Concentrations, amounts, and other numerical data may be expressed or presented herein in a range format. It is to be understood that such a range format is used merely for convenience and brevity and thus should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. As an illustration, a numerical range of “about 1 to about 5” should be interpreted to include not only the explicitly recited values of about 1 to about 5, but also include individual values and sub-ranges within the indicated range. Thus, included in this numerical range are individual values such as 2, 3, and 4 and sub-ranges such as from 1-3, from 2-4, and from 3-5, etc., as well as 1, 2, 3, 4, and 5, individually.

This same principle applies to ranges reciting only one numerical value as a minimum or a maximum. Furthermore, such an interpretation should apply regardless of the breadth of the range or the characteristics being described.

The Invention

The present invention provides stress regulated semiconductor devices and methods associated therewith. Such devices can provide more effective cooling than traditional devices, and as such can be operated at a higher operational power. In one aspect, a vertical design for a semiconductor device can be utilized. One example of a vertical design semiconductor is a vertical stack LED. Much of the following discussion is directed to vertical stack LED devices for convenience. It is noted that this is for convenience sake, and that any type of semiconductor device and/or semiconductor configuration or design is considered to be within the present scope.

One potential technique for cooling a vertical stack LED is the use of a copper coated wafer to provide an integrated heat spreader that is intimately in contact with the semiconductor material. One problem, however, exists due to the difference in the coefficient of thermal expansion (CTE) between copper and many semiconductor materials. There can be a 3 times difference in the CTE of copper compared to a semiconductor material such as silicon. When such an LED is operated at high temperature, the copper expands and contracts to a much greater extent than semiconductor materials for a given temperature change, and can result in microcracks, delamination, and other defects at the interface between the copper and the semiconductor materials. These microcracks can lead to LED failure over time.

In addition to operational failures, in some cases defects can be introduced into a semiconductor device during the manufacturing process. For example, one technique of manufacturing may be to couple a metal heat spreader to a semiconductor material by soldering. Thermal mismatch between these materials during soldering can cause defects, cracking, delamination, and the like to occur or begin to occur.

The inventors have discovered that various materials can be used to moderate the CTE mismatch between a heat spreading material such as copper and a semiconductor, and thus decrease the interface stress there between due to temperature cycling during manufacture and/or use. Such materials can include, without limitation, various forms of diamond, graphite, boron nitrides, and the like. As an additional advantage, these materials tend to be good thermal conductors, and thus facilitate the movement of heat from the semiconductor. Much of the following discussion is directed to diamond materials for convenience, and it is noted that any material capable of moderating the CTE between disparate materials should be considered to be within the present scope.

Semiconductor devices according to aspects of the present invention can be utilized in a variety of applications, including LEDs, laser diodes, p-n junction devices, p-i-n junction devices, SAW and BAW filters, and the like. In one aspect, the semiconductor device is an LED device. In one specific aspect, the semiconductor device is an LED device with a vertical stack configuration.

In one aspect, as is shown in FIG. 1, a stress regulated semiconductor device 10 can include a semiconductor layer 12, a carbon layer 14 formed on the semiconductor layer 12, and a heat spreader 16 coupled to the carbon layer 14 opposite the semiconductor layer 12. The carbon layer 14 is operable to reduce the CTE difference between the semiconductor layer 12 and the heat spreader 16 to less than or equal to about 10 ppm/° C. In another aspect, the carbon layer is operable to reduce the CTE difference between the semiconductor layer and the heat spreader to less than or equal to about 5 ppm/° C. Additionally, the carbon layer can be conductive, non-conductive, or semiconductive, depending on the design of the device. It should be noted that in FIG. 1 and all following FIGs., the semiconductor layer 12 can be one or more layers, junctions, structures, and the like.

The carbon layer can be a single carbon layer or multiple carbon layers, and can include other materials or material layers such as, for example, carbide formers. The term “stress regulating interface layer” can be used to describe one or more carbon layers and any associated materials or material layers therewith. For example, in one aspect a stress regulating interface layer can include a carbon layer and a carbide former.

One benefit of the vertical stack design relates to the placement of electrical contacts in association with the semiconductor. As opposed to more traditional designs, electrical contacts in a vertical stack LED are located on opposite sides of the semiconductor from one another. This allows a linear flow of current from one electrical contact to the other. As is shown in FIG. 2, for example, a vertical stack device 20 can include a semiconductor layer 12, a carbon layer 14 formed on the semiconductor layer, and a heat spreader layer 16 formed on the carbon layer opposite the semiconductor layer. In addition, an electrical contact 18 can be coupled to the semiconductor layer on an opposite side from the heat spreader layer 16. In this case, the carbon layer is conductive to allow the carbon layer and/or the heat spreader layer to act as the other electrical contact. Thus, electrical current flows linearly from one electrical contact to the other. It should be noted that, in some aspects, a second electrical contact in addition to the carbon layer and/or the heat spreader layer can be coupled to the device.

Various additional layers are also contemplated for inclusion in devices according to aspects of the present invention. For example, for many applications, including light-generating devices, it can be beneficial to include a reflective layer positioned to focus and/or direct light. As one example, as is shown in FIG. 3, an LED device 30 can include a reflective layer 32 disposed between the carbon layer 14 and the semiconductor layer 12. Light generated in the semiconductor layer of the vertical stack LED device can be transmitted in multiple directions. One portion of the light can be transmitted forward through the semiconductor layer 12 and out of the device in a direction away from the heat spreader layer 16. Another portion can be transmitted from the semiconductor layer 12 toward the heat spreader layer 16 and the carbon layer 14. Thus the reflective layer 32 can function to reflect at least a portion of this light back through the semiconductor layer and out of the LED, thus increasing the light output of the device. Depending on the optical properties of the particular diamond layer used, the reflective layer can be disposed between the semiconductor layer and the carbon layer as shown, or it can be disposed between the carbon layer and the heat spreader layer (not shown).

In some aspects, it can be beneficial to provide an interlayer between the carbon layer and another layer that the carbon layer is bonded to. For example, a carbide former layer can improve the bonding between a carbon material such as diamond and a variety of other materials. As is shown in FIG. 4, for example, a carbide former layer 42 (i.e. interlayer) can be disposed between the carbon layer 14 and the reflective layer 32 in order to improve the coupling of the carbon layer to the reflective layer. In another aspect, as is shown in FIG. 5, a carbide former layer 42 can be disposed between the carbon layer 14 and the heat spreader layer 16 in order to improve the coupling of the heat spreader layer to the carbon layer. A carbide former layer can also be utilized between a carbon layer and a semiconductor layer (not shown).

Additionally, the CTE mismatch can be further moderated by utilizing multiple carbon layers. Furthermore, in some aspects it can be beneficial to alternate additional layers in between multiple carbon layers. For example, in one aspect a stack of multiple carbon layers can include carbide former layers interspersed between the carbon layers. In one specific aspect, a stress regulating interface layer can include multiple carbon layers having titanium layers interspersed therebetween to provide improved CTE matching between the heat spreader and the semiconductor layer. In one specific aspect, a stress regulating interface layer can include alternating layers of DLC and a carbide former such as Ti to improve CTE matching.

In addition to diamond layers, diamond particles 64 can also be utilized to reduce the CTE mismatch between the metal heat spreader and the semiconductor layer. As is shown in FIG. 6, for example, a stress regulated semiconductor device 60 can include a semiconductor layer 12 and a heat spreader layer 62 formed on the semiconductor layer 12. Diamond particles 64 are uniformly disposed within the metal heat spreader layer 62. The presence of the diamond particles can reduce the CTE mismatch between the semiconductor layer and the heat spreader layer. As is shown in FIG. 7, the diamond particles 64 can also be arranged in a monolayer. In one aspect, the diamond particles are operable to reduce the CTE difference between the semiconductor layer and the metal matrix to less than or equal to about 10 ppm/° C. In another aspect, the diamond particles are operable to reduce the CTE difference between the semiconductor layer and the metal matrix to less than or equal to about 5 ppm/° C. It can be beneficial to form the heat spreader layer including the diamond particles on the semiconductor layer during manufacture of the semiconductor device, as opposed to making a diamond monolayer/metal heat spreader device separately for later attachment, as the soldering step is avoided.

In another aspect of the present invention, a stress regulated semiconductor device can be made according to the following method. As is shown in FIG. 8, a carbon layer 82 is formed on a semiconductor layer 84 having a substrate 86 such as sapphire. In one specific aspect, the semiconductor layer can include GaN. In some aspects, a carbide former layer can be deposited between the carbon layer 82 and the semiconductor layer 84 to improve bonding as has been described (not shown). As is shown in FIG. 9, a heat spreader layer 92 is formed on the carbon layer 82. In some aspects, a carbide former layer can be deposited on the carbon layer 82 to improve bonding with the heat spreader layer 92 as has been described (not shown). Additionally, the heat spreader layer can be thickened to improve the thermal conductivity and/or physical stability of the device. The substrate 86 can be removed as is shown in FIG. 10, and in some aspects, subsequent semiconductive structures can be deposited on the exposed surface of the semiconductor layer 84. The substrate can be removed by a variety of known methods, including laser splitting, mechanical removal, chemical etching, and the like. In some aspects, the exposed surface of the semiconductor layer can be leveled or planarized to improve subsequent deposition thereupon. Note that the device is shown rotated 180° in FIG. 10 for clarity.

It should be noted that in aspects of the present disclosure, at least a first and a second electrode can be coupled to the LED. In one aspect, for example, a first electrode can be coupled to one side of the semiconductor layer opposite the diamond-like carbon layer, and a second electrode can be coupled to the heat spreader side of the LED. In some aspects, a metal heat spreader can be utilized as an electrode.

In another aspect of the present invention, a method for reducing stress induced defects in a semiconductor device is provided. Such a method can include forming a diamond layer on a semiconductor layer and coupling a heat spreader layer to the diamond layer opposite the semiconductor layer. The diamond layer reduces the coefficient of thermal expansion difference between the semiconductor layer and the heat spreader to less than or equal to about 10 ppm/° C. In one aspect, the method can additionally include forming a reflective layer between the diamond layer and the semiconductor layer. As has been described, in some aspects a carbide former layer can be formed between the diamond layer and the reflective layer. In other aspects, a carbide former layer can be formed between the diamond layer and the heat spreader layer. In yet another aspect, coupling the heat spreader to the diamond layer includes forming the heat spreader on the diamond layer.

Numerous types of carbon materials are contemplated for use as carbon layers according to aspects of the present invention. Non-limiting examples include amorphous diamond, diamond-like carbon, polycrystalline diamond, crystalline diamond, single crystal diamond, graphite, and the like. In one aspect, the carbon layer can be an amorphous diamond layer. In another aspect, the carbon layer can be a diamond-like carbon layer. It should be noted that any type of carbon layer can be utilized provided the layer can be formed on a semiconductor layer.

In one aspect, improved CTE matching can be achieved by utilizing a stress regulating interface layer having a carbon layer with an amorphous atomic structure. Examples of such amorphous materials can include diamond-like carbon, amorphous diamond, and the like. Without intending to be bound by any scientific theory, amorphous materials such as diamond-like carbon have a high elastic or yield limit due to their non-crystalline structure. Thus when disposed between two rigid structures such as a heat spreader and a semiconductor during heating and cooling, the amorphous structure of materials such as diamond-like carbon can absorb the expansion and contraction differences between these materials as they expand and contract at different rates.

The carbon layers according to aspects of the present invention can be of any thickness that would allow thermal cooling and CTE mismatch moderation of a semiconductor device. Thicknesses can vary depending on the application and the semiconductor device configuration. For example, greater cooling requirements may require thicker carbon layers. The thickness may also vary depending on the material used in the carbon layer. In some aspects, particularly those where the thickness of the device is to be minimized, it can be beneficial to utilize a carbon layer that is no thicker than necessary for the application. That being said, in one aspect a carbon layer may be from about 10 microns to about 300 microns thick. In another aspect, a carbon layer may be less than or equal to about 10 microns thick. In yet another aspect, a carbon layer may be from about 50 microns to about 100 microns thick. In a further aspect, a carbon layer may be greater than about 50 microns thick. In yet another aspect, the carbon layer can be from about 1 micron to about 30 microns thick. In a further aspect, the carbon layer can be from about 5 microns to about 30 microns thick. In yet a further aspect, the carbon layer can be less than about 1 micron thick. In one aspect, the carbon layer can be from about 0.1 microns to about 10 microns thick. In another aspect, the carbon layer can be from about 0.5 microns to about 2 microns thick. In yet another aspect, the carbon layer can be at least about 300 nm thick. In another aspect, the carbon layer can be at least about 500 nm thick.

In one aspect, the carbon layer can be a diamond material such as, for example, crystalline diamond, amorphous diamond, diamond-like carbon, and the like. Diamond materials have excellent thermal conductivity properties that make them ideal for incorporation into semiconductor devices as has been described herein. The transfer of heat that is present in the semiconductor device can thus be accelerated from the device through a diamond material. It should be noted that the present invention is not limited as to specific theories of heat transmission. As such, in one aspect the accelerated movement of heat from inside the device can be at least partially due to heat movement into and through a diamond layer. Due to the heat conductive properties of diamond, heat can rapidly spread laterally through the diamond layer and to the edges of a semiconductor device. Heat present around the edges will be more rapidly dissipated into the air or into surrounding structures, such as heat spreaders or device supports. Additionally, the diamond layer can thermally conduct heat to the metal heat spreader layer that is intimately contacted therewith. Because the thermal conductivity of diamond is greater than the thermal conductivity of a semiconductor layer to which it is thermally coupled, a heat sink is established by the diamond layer. Thus heat that builds up in the semiconductor layer is drawn into the diamond layer and spread laterally to be transferred into the metal heat spreader. Such accelerated heat transfer can result in semiconductor devices with much cooler operational temperatures. Additionally, the acceleration of heat transfer not only cools a semiconductor device, but may also reduce the heat load on many electronic components that are spatially located nearby the semiconductor device.

It should be understood that the following is a very general discussion of diamond deposition techniques that may or may not apply to a particular layer or application, and that such techniques may vary widely between the various aspects of the present invention. Additionally, and as has been noted, other materials such as boron nitride and graphite are included within the present scope. The following deposition techniques should also be applied to those materials where applicable. Generally, diamond layers may be formed by any means known, including various vapor deposition techniques. Any number of known vapor deposition techniques may be used to form these diamond layers. Common vapor deposition techniques include chemical vapor deposition (CVD) and physical vapor deposition (PVD), although any similar method can be used if similar properties and results are obtained. In one aspect, CVD techniques such as hot filament, microwave plasma, oxyacetylene flame, rf-CVD, laser CVD (LCVD), metal-organic CVD (MOCVD), laser ablation, conformal diamond coating processes, and direct current arc techniques may be utilized. Typical CVD techniques use gas reactants to deposit the diamond or diamond-like material in a layer, or film. These gases generally include a small amount (i.e. less than about 5%) of a carbonaceous material, such as methane, diluted in hydrogen. A variety of specific CVD processes, including equipment and conditions, as well as those used for semiconductor layers, are well known to those skilled in the art. In another aspect, PVD techniques such as sputtering, cathodic arc, and thermal evaporation may be utilized. Additionally, molecular beam epitaxy (MBE), atomic layer deposition (ALD), and the like can additionally be used. Further, specific deposition conditions may be used in order to adjust the exact type of material to be deposited, whether DLC, amorphous diamond, or pure diamond.

In some aspects a nucleation enhancer layer or carbide former layer can be formed on the growth surface of a substrate in order to improve the quality and deposition time of the diamond layer. As has been described, the diamond layer can be deposited on various material layers, such as a semiconductor layer or reflective layer. In one aspect, a diamond layer can be formed by depositing applicable nuclei, such as diamond nuclei, on a diamond growth surface of a substrate and then growing the nuclei into a film or layer using a vapor deposition technique. In one aspect of the present invention, a nucleation enhancer layer can be coated upon the substrate to enhance the growth of the diamond layer. Diamond nuclei are then placed upon the nucleation enhancer layer, and the growth of the diamond layer proceeds via CVD.

A variety of suitable materials will be recognized by those in skilled in the art which can serve as a nucleation enhancer. In one aspect of the present invention, the nucleation enhancer may be a material selected from the group consisting of metals, metal alloys, metal compounds, carbides, carbide formers, and mixtures thereof. In another aspect, the nucleation enhancer layer can be a carbide former layer including a carbide former material. Examples of carbide former materials may include, without limitation, tungsten (W), tantalum (Ta), titanium (Ti), zirconium (Zr), chromium (Cr), molybdenum (Mo), silicon (Si), manganese (Mn), vanadium (V), niobium (Nb), hafnium (Hf), and the like, including combinations thereof. Additionally, examples of carbides include tungsten carbide (WC), silicon carbide (SiC), titanium carbide (TiC), zirconium carbide (ZrC), and mixtures thereof among others. In one specific aspect, the carbide former layer can be Ti. In another specific aspect, the carbide former layer can be Cr. It should be noted that a carbide former layer can be utilized to enhance the deposition of a diamond layer, a carbon layer, a boron nitride layer, or an additional material such as a heat spreader material upon one or more of the aforementioned layers. Additionally, a carbide former layer can be utilized to improve bonding between layers, and many not necessarily involve enhanced nucleation in all cases. In one specific aspect, useful carbide formers can include Ti, W, TiW, Cr, Pt, Zr, V, and the like.

A nucleation enhancer layer or a carbide former layer, when used, is a layer that is thin enough that it does not to adversely affect the thermal transmission properties of the device. In one aspect, the thickness of these layers may be less than about 0.5 micrometers. In another aspect, the thickness may be less than about 10 nanometers. In yet another aspect, the thickness is less than about 5 nanometers. In a further aspect of the invention, the thickness is less than about 3 nanometers. In one aspect, the thickness is from about 50 nm to about 500 nm. In yet another aspect, the thickness is about 100 nm.

Diamond materials having higher proportions of sp3 bonds have higher thermal conductivity while moderating CTE mismatch between the heat spreader and the semiconductor layer. Various methods may be employed that can affect the sp3 content of the diamond in the diamond layer that is created by vapor deposition techniques. For example, reducing the methane flow rate and increasing the total gas pressure during the early phase of diamond deposition can decrease the decomposition rate of carbon, and increase the concentration of hydrogen atoms. Thus a significantly higher percentage of the carbon will be deposited in a sp³ bonding configuration, and thus the quality of the diamond nuclei formed can be increased. Additionally, the nucleation rate of diamond particles deposited on a growth surface of the substrate or the nucleation enhancer layer can be increased in order to reduce the amount of interstitial space between growing diamond particles. Examples of ways to increase nucleation rates include, but are not limited to; applying a negative bias in an appropriate amount, often about 100 volts, to the growth surface; polishing the growth surface with a fine diamond paste or powder, which may partially remain on the growth surface; and controlling the composition of the growth surface such as by ion implantation of C, Si, Cr, Mn, Ti, V, Zr, W, Mo, Ta, and the like by PVD or PECVD. PVD processes are typically at lower temperatures than CVD processes and in some cases can be below about 250° C. such as about 150° C. Other methods of increasing diamond nucleation will be readily apparent to those skilled in the art.

In one aspect of the present invention, the carbon layer may be formed as a conformal diamond layer. Conformal diamond coating processes can provide a number of advantages over conventional diamond film processes. Conformal diamond coating can be performed on a wide variety of substrates, including non-planar substrates. A growth surface can be pretreated under diamond growth conditions in the absence of a bias to form a carbon film. The diamond growth conditions can be conditions that are conventional CVD deposition conditions for diamond without an applied bias. As a result, a thin carbon film can be formed which is typically less than about 100 angstroms. The pretreatment step can be performed at almost any growth temperature such as from about 200° C. to about 900° C., although lower temperatures below about 500° C. may be preferred. Without being bound to any particular theory, the thin carbon film appears to form within a short time, e.g., less than one hour, and is a hydrogen terminated amorphous diamond.

Following formation of the thin carbon film, the growth surface may then be subjected to diamond growth conditions to form a conformal diamond layer. The diamond growth conditions may be those conditions which are commonly used in traditional CVD diamond growth. However, unlike conventional diamond film growth, the diamond film produced using the above pretreatment steps results in a conformal diamond film that typically begins growth substantially over the entire growth surface with substantially no incubation time. In addition, a continuous film, e.g. substantially no grain boundaries, can develop within about 80 nm of growth. Diamond layers having substantially no grain boundaries may move heat more efficiently than those layers having grain boundaries.

Additionally, in some aspects the carbon layer can be a conductive carbon layer such as a conductive diamond layer. Various techniques may be employed to render a diamond layer conductive. Such techniques are known to those of ordinary skill in the art. For example, various impurities may be doped into the crystal lattice of the diamond layer. Such impurities may include elements such as Si, B, P, N, Li, Al, Ga, etc. In one specific aspect, for example, the diamond layer may be doped with B. Impurities may also include metallic particles within the crystal lattice, provided they do not interfere with the function of the device, such as by blocking light emitted from an LED.

Various semiconductor materials are contemplated that can be used in the devices of the present invention. The semiconductor layer may include any material that is suitable for forming electronic devices, semiconductor devices, or the like. Many semiconductors are based on silicon, gallium, indium, and germanium. Suitable materials for the semiconductor layer can include, without limitation, silicon, silicon carbide, silicon germanium, gallium arsenide, gallium nitride, germanium, zinc sulfide, gallium phosphide, gallium antimonide, gallium indium arsenide phosphide, aluminum phosphide, aluminum arsenide, aluminum gallium arsenide, gallium nitride, boron nitride, aluminum nitride, indium arsenide, indium phosphide, indium antimonide, indium nitride, indium gallium nitride, and composites thereof. In one aspect, however, the semiconductor layer can include silicon, silicon carbide, gallium arsenide, gallium nitride, gallium phosphide, aluminum nitride, indium nitride, indium gallium nitride, aluminum gallium nitride, or composites of these materials. In one specific aspect, the semiconductor material includes gallium nitride. In another specific aspect, the semiconductor material includes aluminum nitride. In yet another aspect, the semiconductor material includes indium nitride. In a further aspect, the semiconductor includes (Al, Ga, In)N. In yet another aspect, the semiconductor material can include elements selected from Group II elements to Group VI elements.

Additionally, semiconductor materials may be of any structural configuration known, for example, without limitation, cubic (zincblende or sphalerite), wurtzitic, rhombohedral, graphitic, turbostratic, pyrolytic, hexagonal, amorphous, or combinations thereof. As such, the semiconductor layer can be formed by any method known to one of ordinary skill in the art. Various known methods of vapor deposition can be utilized, as has been described. Additionally, surface processing may be performed between any of the deposition steps described in order to provide a smooth surface for subsequent deposition. Such processing may be accomplished by any means known, such as by chemical etching, polishing, buffing, grinding, etc.

Various materials are contemplated for use as a substrate upon which the semiconductor layer can be deposited. Any material that is suitable for this purpose is considered to be within the present scope. Non-limiting examples of such materials include Al₂O₃, Si, SiC, GaAs, GaP, AlP, GaN, graphite, hBN, or diamond. Other examples can include a nitride, a phosphide, or an arsenide including at least one cation such as B, Al, Ga, In, Be, or Mg.

The reflective layer can be made from a variety of reflective materials. Non-limiting examples include Ag, Al, Ni, Co, Pd, Pt, Au, Zn, Sn, Sb, Pb, Cu, CuAg, NiAg, and alloys thereof. The thickness of the reflective layer is not specifically limited, as long as the purpose for light guiding can be realized and the light-illumination efficiency can be increased. In one aspect, the thickness of the reflective layer can be from about 100 nm to about 500 nm. In another aspect, the thickness can be about 200 nm.

Various materials are contemplated for use in the heat spreader layer. Any material that can be utilized in the devices according to aspects of the present invention are considered to be within the present scope. Nonlimiting examples of such materials can include aluminum, copper, tin, tungsten, nickel, titanium, gold, silver, platinum, Al₂O₃, AN, Si₃N₄, Si, glass, and combinations and alloys thereof, and the like, including mixtures and alloys thereof. In one aspect, the heat spreader can be a metal heat spreader. In one specific aspect, the heat spreader includes copper. Additionally, the heat spreader materials can be applied to the device using any deposition technique. In one aspect, for example, the material can be deposited by sputtering. In another aspect, the heat spreader can be soldered to the device using, for example, Au or Au—Sn.

Additionally, in some aspects the heat spreader can be a composite material of a metal and diamond particles. In one aspect, the diamonds can be arranged in only a single layer within the metal material. In another aspect, the diamonds can be arranged in multiple single layers throughout the metal material. In yet another aspect, the diamonds can be arranged in more of a randomly distributed pattern throughout the metal. In one aspect, the content of the diamond particles in the composite material can be from about 25 wt % to about 60 wt %. In another aspect, the content of the diamond particles in the composite material can be from about 30% to about 50%. Furthermore, while a variety of metals are contemplated, non-limiting examples include at least one of Cu, Ag, Co, Ni, W, Fe, Ti, Cr, B, and the like, including combinations thereof. The diamond can be natural or synthetic diamond particles. Furthermore, in one aspect the diameter of the diamond can be from about 1 μm to about 1 mm. In one specific aspect, the composite material includes diamond particle impregnated nickel.

The thickness of the composite material is not specially limited, and any useful thickness is considered to be within the present scope. In one aspect, for example, the thickness of the composite material layer can be from about 100 μm to about 500 μm. In another aspect, the layer can be about 150 μm thick. The thermal expansion coefficient of the composite material layer can be properly adjusted according to the needs of a given situation so as to avoid bending or causing an internal defect of the LED due to interfacial stress, which may reduce the yield, increase the manufacturing cost, and increase light attenuation. Accordingly, in one aspect the thermal expansion coefficient of the composite material layer can be from about 2 ppm/° C. to about 10 ppm/° C.

Further, in some aspects, the composite material layer can be polished to an Ra of less than about 1 μm, so as to keep the flatness of the remaining surface to under ±1 mm. The same is polishing can be performed on any type of layer in the LED, including a heat spreader layer.

Following deposition of the heat spreader layer, the thickness of the layer can be increased via a thickening process. Such thickening can increase the thermal conductivity of the device, provide for additional structural support for the semiconductor materials, facilitate device handling and attachment to other substrates, and the like. As one example, a temporary support substrate can be removed from the semiconductor device once the heat spreader layer has been increased to a thickness that is capable of providing adequate support. As such, in one aspect a heat spreader has a minimum thickness for supporting the semiconductor material such that bowing does not occur. Although any method of thickening is contemplated, in one aspect a metal heat spreader can be thickened by further sputtering of the heat spreader material and/or an additional metal material. In another aspect, the metal heat spreader layer can be thickened by electroplating additional metal material thereupon. The metal material can be the same or different from the metal material originally sputtered onto the device. In some aspects, a monolayer of diamond particles can be disposed on the sputtered metal heat spreader layer. Subsequent electroplating will thicken the metal heat spreader layer, thus incorporating the diamond particles within the metal material.

In another aspect of the present disclosure, a transparent diamond-like carbon layer can be formed on one side of the semiconductive layer, so as to dissipate heat generated from the phosphor layer of the LED, and increase the light-emitting efficiency and lifetime of the LED. For example, the transparent diamond-like carbon layer can be formed on the side of the semiconductor layer opposite the diamond-like carbon layer, or in other words, on the side opposite from the heat spreader. The transparent diamond like carbon layer can be formed by any deposition method, such as, for example, a plasma chemical vapor deposition (PECVD) method. One way of forming a diamond-like carbon layer that is transparent is to include hydrogen atoms in the deposited layer. In one aspect, the content of the hydrogen atoms can be from about 15 at % to about 40 at % based on the total amount of the transparent diamond like carbon layer, so as to increase the heat-dissipating rate and light emitting efficiency.

According to a conventional LED designs, the positive and the negative electrodes are located on the same side to the semiconductive layer. Due to the dielectric nature of common sapphire substrates, electrical current generated by the semiconductive layer flows vertically down and then turns to flow horizontally. As a result, a current accumulation occurs at the inner corner of the semiconductive layer, so as to hinder the electron layer and the hole layer of the P-N surface. This can cause the illumination efficiency to decrease. A hot point is also generated when current accumulation occurs in the semiconductive layer, which may cause a defect to the crystalline of the semiconductive layer and reduce the lifespan of the LED. Since the thermal expansion coefficient of the metallic reflective layer is greater than that of a semiconductive layer such as GaN, stress can incur at the interface. Therefore, for a conventional LED, an electrical current may proceed along the path with minimum resistance while electrified, and a portion having greater stress may result in rising temperature, so as the crystal lattice can be expanded by the metallic reflective layer. As shown in FIGS. 11A and 11B, particularly with a high frequency of turning on and off the LED, defects can be induced by the repeated movements of the crystal lattice of the semiconductive layer, which results in a rapid decrease of the brightness of the LED.

In contrast, for the vertical LED of the present disclosure, heat generated by the LED during illumination can be dissipated/conducted away rapidly due to the diamond-like carbon layer and/or the diamond-containing heat spreader having a high thermal conductivity, and thus can avoid problems such as light attenuation and short lifespan due to defects of the crystalline semiconductor material caused by the non-uniformity of the inner electrical current. Since the stress at the interface is extensively reduced, problems such as light attenuation and short lifespan due to defects of the crystalline lattice caused by the non-uniformity of the inner electrical current can be avoided, as shown in FIG. 12.

As a result, the current vertical LED allows the realization of light emitting diodes of a large scale (>1 mm), a large current (>1 A/mm2), and a large power (>10 W), which cannot be achieved by conventional light emitting diodes having a curving current therein. Furthermore, the vertical LED of the present disclosure has advantages of high luminance, high brightness, high heat-dissipation rate (due to the excellent heat conductivity of the diamond-like carbon layer) during illumination, and freedom from internal defects, so as to realize a long lifetime.

Furthermore, as for the composite material layer (i.e. the heat spreader) and the diamond-like carbon layer in the present invention, analysis results show that the thermal expansion coefficient of the present LED is properly controlled, and the thermal resistance is reduced (See FIG. 13). As has been described, the coefficient of thermal expansion (CTE) can be adjusted depending on the diameter and the volume percentage of the diamond in a heat spreader composite material. In order to obtain a good coefficient of thermal expansion (e.g. about 2-10 ppm/° C.), the volume percentage of the diamond is can be about 30-50 Vol %, as shown in FIG. 14, and the diameter of the diamond can be as is shown in FIG. 15.

Therefore, according to the LED provided by the method of the present example, a light emitting diode of large scale (>1 mm), large current (>1 A/mm2), and large power (>10 W) can be realized, which cannot be obtained by parallel connection of plural conventional light emitting diodes that have a curving current therein. Furthermore, the vertical light emitting diode and/or the method of fabricating the same of the present example have advantages of high luminance, high brightness, high heat-dissipation rate (due to the excellent heat conductivity of the diamond-like carbon layer) during illumination, and free of internal defects so as to realize a long lifetime, which cannot be obtained by a conventional light emitting diode.

EXAMPLES

The following examples illustrate various techniques of making semiconductor devices according to aspects of the present invention. However, it is to be understood that the following are only exemplary or illustrative of the application of the principles of the present invention. Numerous modifications and alternative compositions, methods, and systems can be devised by those skilled in the art without departing from the spirit and scope of the present invention. The appended claims are intended to cover such modifications and arrangements. Thus, while the present invention has been described above with particularity, the following Examples provide further detail in connection with several specific embodiments of the invention.

Example 1

A 2 inch sapphire wafer is deposited with epitaxial GaN by MOCVD (metal organic chemical vapor deposition). Trimethylgallium is used as the Ga source gas and ammonia is added to supply nitrogen atoms. Hydrogen is also added in order to dilute the gas and to gasify Ga or N atoms if they are located in unstable sites on the lattice. A multiple layered semiconductor structure is made by n-doping with Si on the sapphire followed by p-doping with Mg to form a junction. Quantum wells and intrinsic layers can be introduced between the p-doped layer and the n-doped layer. The top surface of the p-doped layer is sputtered with a reflective layer of Ag to a thickness of about 200 nm. The reflective layer is then sputtered with a nucleation enhancing layer of Ti to about 50 nm thick.

Subsequently, amorphous diamond is deposited on the nucleation enhancing layer to a thickness of about 1 μm by cathodic arc deposition. An additional nucleation enhancing layer of Ti is sputtered on the amorphous diamond layer to a thickness of about 50 nm, followed by sputtering of a Cu metal layer. The device is then removed from the deposition chamber and immersed in an electrolyte solution where the Cu layer is thickened by electroplating. A region of the GaN layer is then laser irradiated to separate the sapphire wafer from the GaN layer. The newly exposed n-doped GaN surface is then sputtered with Au as electrode at one corner. This will form a vertical stack LED with top and bottom electrodes.

Example 2

A 2 inch sapphire wafer is deposited with epitaxial GaN by MOCVD (metal organic chemical vapor deposition). Trimethylgallium is used as the Ga source gas and ammonia is added to supply nitrogen atoms. Hydrogen is also added in order to dilute the gas and to gasify Ga or N atoms if they are located in unstable sites on the lattice. A multiple layered semiconductor structure is made by n-doping with Si on the sapphire followed by p-doping with Mg to form a junction. Quantum wells and intrinsic layers can be introduced between the p-doped layer and the n-doped layer.

The top surface of the p-doped layer is cosputtered with graphite and Ag to form a reflective layer. The graphite acts to reduce the CTE of the reflective layer. In this case, the CTE can be graded by controlling Ag/C ratio. Ag coating is then resumed without graphite. The Ag layer is then thickened by electroplating with Cu or Ag.

Example 3

A 2 inch sapphire wafer is deposited with epitaxial GaN by MOCVD (metal organic chemical vapor deposition). Trimethylgallium is used as the Ga source gas and ammonia is added to supply nitrogen atoms. Hydrogen is also added in order to dilute the gas and to gasify Ga or N atoms if they are located in unstable sites on the lattice. A multiple layered semiconductor structure is made by n-doping with Si on the sapphire followed by p-doping with Mg to form a junction. Quantum wells and intrinsic layers can be introduced between the p-doped layer and the n-doped layer.

The top surface of the p-doped layer is cosputtered with graphite and Ag to form a reflective layer. The graphite acts to reduce the CTE of the reflective layer. In this case, the CTE can be graded by controlling Ag/C ratio. Ag coating is then resumed without graphite. A monolayer of micron diamond particles is spread across the Ag layer, and a Cu layer is electroplated there upon to incorporate the diamond particles. The diamond particle monolayer functions to further reduce the CTE mismatch and increase of thermal conductivity.

Example 4

A 2 inch sapphire wafer is deposited with epitaxial GaN by MOCVD (metal organic chemical vapor deposition). Trimethylgallium is used as the Ga source gas and ammonia is added to supply nitrogen atoms. Hydrogen is also added in order to dilute the gas and to gasify Ga or N atoms if they are located in unstable sites on the lattice. A multiple layered semiconductor structure is made by n-doping with Si on the sapphire followed by p-doping with Mg to form a junction. Quantum wells and intrinsic layers can be introduced between the p-doped layer and the n-doped layer.

The top surface of the p-doped layer is sputtered with a reflective layer of Ag to a thickness of about 200 nm. A Cu metal layer is sputtered onto the Ag layer. A monolayer of micron diamond particles is spread across the sputtered Cu layer, and the Cu layer is thickened by electroplating to incorporate the diamond particles to reduce the CTE mismatch and increase of thermal conductivity.

Example 5

An LED wafer with GaN on sapphire is metalized with a gold layer. An ethanol-diluted wax layer is spread across the top of the gold layer. Diamond particles of about 150 μm in size are pressed across the layer, and excess diamond particles not adhered to the layer are removed. The wafer is used as a cathode and is immersed in a liquid electrolyte with copper as the anode, and the wafer is electroplated to cover the diamond particles in-situ with copper. The sapphire layer is split by laser irradiation and removed, and the exposed GaN surface is coated with an ITO electrode except for a small area where gold is coated as an anode. The copper layer is used as the cathode. Thus vertical stack LED is made with electrodes on the opposing sides.

Example 6

An LED wafer having multiple layers of doped GaN on sapphire is sputtered with a reflector layer of Ag, and then a nucleation enhancer layer of Ti. An electrically conductive amorphous diamond layer is then deposited on the Ti layer by cathodic arc. The amorphous diamond is metalized by sputtering with Cr followed by Cu. The Cu layer is thickened by conventional electroplating, resulting in copper bonded GaN.

Example 7

A 2 inch sapphire wafer is deposited with epitaxial GaN by MOCVD. Trimethylgallium is used as the Ga source gas and ammonia is added to supply nitrogen atoms. Hydrogen is also added in order to dilute the gas and to gasify Ga or N atoms if they are located in unstable sites on the lattice. A multiple layered semiconductor structure is made by n-doping with Si on the sapphire followed by p-doping with Mg to form a junction. Quantum wells and intrinsic layers can be introduced between the p-doped layer and the n-doped layer. The top surface of the p-doped layer is sputtered with a reflective layer of Ag to a thickness of about 200 nm. The reflective layer is then sputtered with a nucleation enhancing layer of Ti to about 50 nm thick.

Subsequently, amorphous diamond is deposited on the nucleation enhancing layer to a thickness of about 1 μm by cathodic arc deposition. An additional nucleation enhancing layer of Ti is sputtered on the amorphous diamond layer to a thickness of about 50 nm, followed by sputtering of a Cu metal layer. The device is then removed from the deposition chamber and immersed in an electrolyte solution including Ni and diamond particles for Ni-diamond layer coating by electroplating. The diamond content is about 30 Vol %. A region of the GaN layer is then laser irradiated to separate the sapphire wafer from the GaN layer. The newly exposed n-doped GaN surface is then sputtered with Au as electrode at one corner. This will form a vertical stack LED with top and bottom electrodes.

Of course, it is to be understood that the above-described arrangements are only illustrative of the application of the principles of the present invention. Numerous modifications and alternative arrangements may be devised by those skilled in the art without departing from the spirit and scope of the present invention and the appended claims are intended to cover such modifications and arrangements. Thus, while the present invention has been described above with particularity and detail in connection with what is presently deemed to be the most practical and preferred embodiments of the invention, it will be apparent to those of ordinary skill in the art that numerous modifications, including, but not limited to, variations in size, materials, shape, form, function and manner of operation, assembly and use may be made without departing from the principles and concepts set forth herein. 

1. A method for fabricating a vertical light emitting diode, comprising: providing a substrate; forming a semiconductive layer on the substrate, the semiconductive layer including a compound made of elements selected from Group II elements to Group VI elements; forming a metallic reflective layer coupled to the semiconductive layer; forming at least one interlayer and at least one diamond-like carbon layer coupled to the metallic reflective layer; forming a composite material layer coupled to the diamond-like carbon layer; removing the substrate; and forming a first electrode layer and a second electrode layer on a side of the semiconductive layer and a side of the composite material layer respectively.
 2. The method of claim 1, wherein the at least one interlayer and the at least one diamond-like carbon layer are substantially interstacked at one side of the metallic reflective layer.
 3. The method of claim 1, further comprising polishing the composite material layer to about Ra<1 μm.
 4. The method of claim 1, wherein a transparent diamond-like carbon layer is formed on one side of the semiconductive layer opposite to the diamond-like carbon layer.
 5. The method as claimed in claim 4, wherein the transparent diamond like carbon layer includes hydrogen atoms therein, wherein the content of the hydrogen atoms is from about 15 at % to about 40 at % based on the total amount of the transparent diamond-like carbon layer.
 6. The method as claimed in claim 23, wherein the composite material layer is connected with the metallic reflective layer by soldering using Au or Au—Sn at about 300° C. or by a high temperature connecting method.
 7. A vertical light emitting diode, comprising: a semiconductive layer including a compound made of elements selected from Group II elements to Group VI elements; a metallic reflective layer coupled to the semiconductive layer; at least one interlayer; at least one diamond-like carbon layer, wherein the at least one interlayer and the at least one diamond-like carbon layer are interstacked at one side of the metallic reflective layer opposite the semiconductive layer; a composite material layer coupled to the diamond-like carbon layer; and a first electrode layer and a second electrode layer located on a side of the semiconductive layer and a side of the composite material layer respectively.
 8. The vertical light emitting diode of claim 7, wherein the composition of the semiconductive layer is selected from the group consisting of Al₂O₃, Si, SiC, GaAs, GaP, AlP, GaN, graphite, hBN, diamond or a combination thereof, or selected from the group consisting of a nitride, a phosphide, or an arsenide including at least one cation selected from B, Al, Ga, In, Be, or Mg.
 9. The vertical light emitting diode of claim 7, wherein the metallic reflective layer includes at least one material selected from the group consisting of Ag, Al, Ni, Co, Pd, Pt, Au, Zn, Sn, Sb, Pb, Cu, CuAg, NiAg, and alloys thereof.
 10. The vertical light emitting diode of claim 7, wherein the thickness of the metallic reflective layer is from about 100 nm to about 500 nm.
 11. The vertical light emitting diode of claim 7, wherein the interlayer includes at least one material selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W, and alloys thereof.
 12. The vertical light emitting diode of claim 7, wherein the thickness of the interlayer is from about 50 nm to about 500 nm.
 13. The vertical light emitting diode of claim 7, wherein the composite material layer comprises a composite material composed of at least one metal and diamond, in which the diamond is substantially arranged in a form of single layer or multi-layers, or the diamond is randomly distributed in the composite material.
 14. The vertical light emitting diode of claim 13, wherein the diamond content in the composite material is from about 25 wt % to about 60 wt %.
 15. The vertical light emitting diode of claim 14, wherein the metal includes at least one material selected from the group consisted of Cu, Ag, Co, Ni, W, Fe, Ti, Cr, and B.
 16. The vertical light emitting diode of claim 7, wherein the composite material layer has a thickness of from about 100 μm to about 500 μm.
 17. The vertical light emitting diode of claim 7, wherein the composite material layer has a thermal expansion coefficient of from about 2 ppm/° C. to about 10 ppm/° C.
 18. The vertical light emitting diode of claim 7, further comprising a transparent diamond like carbon layer located on one side of the semiconductive layer opposite the diamond-like carbon layer.
 19. The vertical light emitting diode of claim 18, wherein the transparent diamond like carbon layer comprises hydrogen atoms therein, wherein the content of the hydrogen atoms is from about 15 at % to about 40 at % based on the total amount of the transparent diamond like carbon layer.
 20. A vertical light emitting diode, comprising: a semiconductive layer comprising a compound made of elements selected from Group II elements to Group VI elements; a metallic reflective layer coupled to the semiconductive layer; a composite material layer coupled to the metallic reflective layer; and a first electrode layer and a second electrode layer locating on a side of the semiconductive layer and a side of the composite material layer respectively. 